Source:http://linkedlifedata.com/resource/pubmed/id/15554651
| Subject | Predicate | Object | Context |
|---|---|---|---|
| pubmed-article:15554651 | rdf:type | pubmed:Citation | lld:pubmed |
| pubmed-article:15554651 | lifeskim:mentions | umls-concept:C0007447 | lld:lifeskim |
| pubmed-article:15554651 | lifeskim:mentions | umls-concept:C0233820 | lld:lifeskim |
| pubmed-article:15554651 | lifeskim:mentions | umls-concept:C1516769 | lld:lifeskim |
| pubmed-article:15554651 | lifeskim:mentions | umls-concept:C0007996 | lld:lifeskim |
| pubmed-article:15554651 | lifeskim:mentions | umls-concept:C1880157 | lld:lifeskim |
| pubmed-article:15554651 | pubmed:issue | 24 | lld:pubmed |
| pubmed-article:15554651 | pubmed:dateCreated | 2004-11-23 | lld:pubmed |
| pubmed-article:15554651 | pubmed:abstractText | Phosphines are traditionally considered as Lewis bases or ligands in transition metal and main group complexes. Despite their electron-rich (lone pair-bearing) nature, an extensive coordination chemistry for Lewis acidic phosphorus centers is being developed; such chemistry provides a new synthetic approach for phosphorus-element bond formation, leading to new types of structures and modes of bonding. Complexes of Ph2P+ with a variety of donor elements (P, N, C) give experimentally short donor-acceptor bond lengths, when compared to other cationic phosphorus Lewis acid complexes. We have calculated that the energy of the lowest unoccupied molecular orbital (LUMO) in Ph2P+ is lower than that of (Me2N)2P+, which partially explains the greater exothermicity of reactions of donors with the diaryl acceptor. Furthermore, the energies required to distort the diphenylphosphenium cation from its ground-state geometry are significantly smaller than those of the diamido cations and, thus, enhance the exothermicity of donor coordination. These computational data, in conjunction with evidence from experimental solid-state structures, indicate that Ph2P+ is a significantly better Lewis acid relative to the more common diaminophosphenium analogues (R2N)2P+ and are used to elucidate the nature of the bonding in donor-phosphenium complexes. | lld:pubmed |
| pubmed-article:15554651 | pubmed:language | eng | lld:pubmed |
| pubmed-article:15554651 | pubmed:journal | http://linkedlifedata.com/r... | lld:pubmed |
| pubmed-article:15554651 | pubmed:status | PubMed-not-MEDLINE | lld:pubmed |
| pubmed-article:15554651 | pubmed:month | Nov | lld:pubmed |
| pubmed-article:15554651 | pubmed:issn | 0020-1669 | lld:pubmed |
| pubmed-article:15554651 | pubmed:author | pubmed-author:RagognaPaul... | lld:pubmed |
| pubmed-article:15554651 | pubmed:author | pubmed-author:MacdonaldChar... | lld:pubmed |
| pubmed-article:15554651 | pubmed:author | pubmed-author:EllisBobby... | lld:pubmed |
| pubmed-article:15554651 | pubmed:issnType | lld:pubmed | |
| pubmed-article:15554651 | pubmed:day | 29 | lld:pubmed |
| pubmed-article:15554651 | pubmed:volume | 43 | lld:pubmed |
| pubmed-article:15554651 | pubmed:owner | NLM | lld:pubmed |
| pubmed-article:15554651 | pubmed:authorsComplete | Y | lld:pubmed |
| pubmed-article:15554651 | pubmed:pagination | 7857-67 | lld:pubmed |
| pubmed-article:15554651 | pubmed:year | 2004 | lld:pubmed |
| pubmed-article:15554651 | pubmed:articleTitle | Computational insights into the acceptor chemistry of phosphenium cations. | lld:pubmed |
| pubmed-article:15554651 | pubmed:affiliation | Department of Chemistry and Biochemistry, University of Windsor, Windsor, Ontario N9B 3P4, Canada. | lld:pubmed |
| pubmed-article:15554651 | pubmed:publicationType | Journal Article | lld:pubmed |